Synthesis and New Applications of DME - a review of alternatives

Transcription

1 Synthesis and New Applications of DME - a review of alternatives Presenter: Helge Holm-Larsen Chairman, International DME Association, IDA 8th NGCS Natal, May 30, 2007 Outline DME & IDA DME Technology DME Applications 1

2 DME at a glance Boiling point, o C Vapor 20 o C, bar 5.1 Liquid 20 o C, kg/m Specific gravity, gas 1.59 International DME Association Objectives: Promote public awareness of DME Provide a platform for international contact Monitor global DME developments Collect and provide all relevant DME information Deliver presentations, organize workshops and conferences Advocate DME to key decision makers Promote and guide development to address obstacles to the market penetration Website: 2

3 DME Technology (XTD) DME = Multi Source Multi Purpose Natural gas Other fossil sources Biomass DME CH3-O-CH3 Power Power Diesel Diesel Gasoline Gasoline LPG LPG Chemical Chemical feedstock feedstock Steam Topsøe Synthesis Gas by 2-step Reforming Oxygen Desulphurisation Prereforming Steam reformer ATR/ secondary reformer Steam Hydrocarbon Syngas BFW 3

4 DME Production from Natural gas by JFE Process CO 2 Natural gas O 2 Syngas Production (ATR) DME Synthesis Separation Purification DME Syngas Production (Auto-Thermal Reformer) 2CH 4 +O 2 +CO 2 3CO+3H 2 +H 2 O Wednesday, DME 11:20Synthesis (Slurry phase reactor, Catalyst) Bossa Nova room 3CO+3H 2 CH 3 OCH 3 +CO 2 Overall reaction 2CH 4 +O 2 CH 3 OCH 3 + H 2 O Gasification - DME from Low- Value Coal or Biomass Low value feedstocks Coal Pet Coke Oil Residue Biomass Wastes Source: Eric Larson Oxygen H2O Gasification Gas Cleanup CO 2 Storage CO, H 2, H 2 S, H 2 O, CO 2 CO2 Removal WGS: CO + H 2 O! H 2 + CO 2 H2S Removal SULFUR RECOVERY High-Value Products Combined Cycle Power Block Fuel Cells Gas Turbines Clean Syngas (H 2 + CO) Electricity Steam Catalytic Synthesis Marketable Byproducts: Sulfur Slag " Gasification is key technology for making clean fuels from coal or biomass and for low-cost CO 2 capture & storage DME,MeOH (or F-T, H 2, chemicals) 4

5 Växjö Värnamo Biomass Gasification Centre (VVCBG) Objective: Växjö A fossil fuel free community # An existing pilot pressurized gasification plant # 4 ton/h dry biomass, 18 MW fuel IGCC pilot plant, MTPD DME # Modified from air blown to oxygen blown # First project: CHRISGAS, Clean Hydrogen-Rich Synthesis Gas # EU biomass gasification research platform Source: T L Gardmark Black Liquor Gasification 5

6 DME from syngas (1) 3 H 2 + CO 2 CH 3 OH + H 2 O (2) H 2 O + CO H 2 + CO 2 (3) 2 CH 3 OH CH 3 OCH 3 + H 2 O DME Production 1 step vs 2 step technology Similar CAPEX (lower than FT) 1 step improves energy efficiency First plants: all two-step processes Technology providers include Haldor Topsøe, Lurgi, Toyo, MGC and JFE Holdings Conventional two-step process Coal Natural gas Biomass Petroleum coke Syngas (CO+H 2 ) Methanol (DME) Methanol and DME Direct or combined processes 6

7 Topsøe Integrated Synthesis Methanol catalyst Purge gas to fuel BFW Steam Methanol from distillation Proprietary dual function catalyst Syngas DME/Methanol/Water to distillation Typical Methanol Equilibrium Outlet Reaction profile Methanol equilibrium Inlet 7

8 Combined MeOH/ DME Equilibrium MeOH + DME equilibrium Outlet Reaction profile Methanol equilibrium Inlet Breaking the equilibrium barrier Outlet MeOH + DME equilibrium Reaction profile Methanol equilibrium Inlet 8

9 Merits of the profiled fixed bed DME reactor concept Dual function catalyst: Breaking the thermodynamic equilibrium barrier Higher conversion No cryogenic separation Lower recycle Lower catalyst/reactor volume Profiled fixed bed: Sequential reaction Each catalyst operating at optimal conditions Maximum reaction rates Minimum catalyst load Reaction specific heat management Low cost High conversion, low recycle Simple reactors Industrially proven reactor concept Slurry Phase DME Reactor 100 MTPD demo unit SU December day runtime 19,520 ton DME DME, CO 2 unreacted CO, H 2 JFE Proprietary catalyst Steam Water Wednesday, 11:20 Slurry Bossa Nova room (Catalyst + Solvent) gas bubble CO, H 2 9

10 Features of slurry phase reactor for DME Pro Good temperature control No diffusion limitation Rapid load response In-line catalyst replacement Con Complicated reactor layout (3 phases) Small catalyst loading fraction Catalyst attrition & distribution DME from Methanol 2 CH 3 OH CH 3 OCH 3 + H 2 O 10

11 MeOH dehydration lay-out Recycle Off-gas DME Product Methanol Methanol dehydration Waste Water Reactor DME Column Waste Water Column Topsøe MeOH dehydration TW1 A TW2 M Adiabatic reactor, delta T ~ 100 C Fuel Grade or Grade AA methanol feed 30% lower feedstock cost with fuel grade MeOH Inlet temperature determined by catalyst Outlet temperature determined by H Efficient heat integration Low investment Robust, easy to operate Simple catalyst load/unload H2 H1 B 11

12 Topsøe dehydration catalyst Acid based catalysis Promoted alumina Surface stabilized material High strength High activity and selectivity Tailored shape and porosity Flexible operation parameters Temperature range C DMK-10 By products Pilot operation Concentration / ppm Fuel grade mode Level for quantitative measurement 0 CH 4 C 2 H 4 C 2 H 6 C 3 H 6 C 3 H 8 Byproduct 12

13 DME Technology Evolution Yesterday: By-product of high temperature methanol synthesis Today: Dehydration of methanol Tomorrow: Integrated approach ( direct ) Slurry bed technology Fixed bed technology Application of DME Propellant LPG (Cooking Fuel) Diesel Power Generation Chemical Intermediate 13

14 DME as Propellant Proven track record: Production ~ MTPY (Propellant grade) Value chain established Permits & standards in place Clean Bill of Health Safe Non toxic Not carcinogenic No ozone depletion Uses of DME Hair spray Spray paints Insecticides Adhesives Industrial feedstock Market share 48% 6% 6% 5% 31% Not a greenhouse gas Miscellaneous 4% Application LPG A commercial gas stove can be used for DME/LPG mixtures without modification Properties DME LPG Vapour Pressure kpa Liquid density kg/m Lower Heating Value MJ/kg Bottle Fill percent Mass per unit volume of bottle kg/m Energy per unit volume of bottle GJ/m

15 Cooking fuel DME recognized (like LPG) as a clean fuel able to reduce indoor air pollution mainly in Asia (India, China) and in Sub- Saharan Africa, WEO, Nov 2006 DME as LPG blend stock DME/LPG blending work (BP, ENI) Supported by World LPG Association Below 20 %v DME, existing LPG infrastructure can be used 20% of world LPG demand = >40 mill ton/year potential DME market World LP Gas Association Supports DME 15

16 DME - The ultimate diesel fuel High cetane Completely SOOTLESS (No smoke) 90% NO x reduction Meets/exceeds new NO x emission standards No sulphur Low HC, CO Quiet combustion Engine/fuel system lower cost than conventional diesel Fuel Distribution: Like LPG Particulate (g/bhp-hr) Pictures courtesy of Volvo Truck Corp and NKK Corp Heavy-duty emissions estimates Diesel '01 DME '95 DME NOx (g/bhp-hr) Progress on DME as Diesel fuel at DTU, Denmark 2007 Eco-Marathon winner (urban car class) 306 km/l Diesel Eq Eco-Marathon winner (prototype class) 780 km/l Diesel Eq. DME combustion chamber Diesel combustion chamber 16

17 DME for Power Generation Combined cycle configuration: Higher thermal efficiency Reduced emission No sulphur, dust, lower NOx. Cost competitive, particularly in smaller markets. Commercially available Chemical Recuperation/GT cycle: 2-3%-point efficiency increase Best for smaller applications (single cycle) Chemical recuperation Picture Courtesy of GE Power Generation in SOFC Direct DME fueled Solid Oxide Fuel Cell E 5 Flue gas P 1 E 1 Ejector recycle X 1 E 2 Potential for Carbon DME/Methanol SOFC Low H increases Air Flow Anode Cathode Catalytic Burner E 3 E 7 K1 Depleted Air Air 17

18 Power Generation in SOFC Solid Oxide Fuel Cell with Methanated DME E 5 Flue gas P 1 E 1 X 1 Methanator DME/Methanol R 1 SOFC Anode Cathode Catalytic Burner E 3 E 7 K1 Depleted Air Air DME Methanation for SOFC Eliminates potential carbon formation problems Eliminates the need for an anode in/out heat exchanger Increases the electric efficiency by 2-3 %-point relative. Reduces the combined heat exchanger duties by 20 % Reduces the air compressor work by 18 % Reduces the fuel cell stack size by approx. 10 % 18

19 DME as Chemical Intermediate DME is an attractive chemical feedstock. It behaves essentially as liquid synthesis gas and may be used for instance in production of: Ammonia Acetic acid and anhydride Short olefins (MTO) Gasoline Synthesis gas (H 2 /CO/CO 2 mixture) Hydrogen Conversion equilibrium vs temperature DME, Methanol 100 Conversion % NH3 Conditions P = 3 bar g O/C ratio = CH4, gasoline, diesel Deg. C 19

20 DME/Methanol-to-Shift Novel Dual Purpose Catalyst CO + H 2 O = CO 2 + H 2 + Q CH 3 OH + H 2 O + Q = CO 2 + 3H 2 DME/Methanol-to-Shift Before After Relative Revamp Revamp Change H2 Production Nm3/h % NG consumption Nm3/h % SMR duty Gcal/h % Methanol consumption kg/h Shift reactor, Tin / Tout C 210 / /

21 Gas to propylene Natural gas Syngas Production Unit Methanol Production Unit DME Unit Propylene The fully commercial MTP process comprises a DME-stage and an olefins stage Omitting the olefins stage from MTP leaves a DME production unit > 3000 MTPD capacity under design/construction Compared to methanol, DME is partly dehydrated better process conditions in the olefin reactor Source: W. Liebner, Lurgi TIGAS Topsøe Integrated Gasoline Synthesis Thursday, 10:50 Europa room Off-gas C 3 -C 4 Synthesis Gas MeOH/DME Synthesis Gasoline Synthesis Separation Gasoline Water Simple process layout Low recycle No methanol condensation / re-evaporation Moderate pressure 21

22 DME Application Evolution Yesterday: Propellant Today: LPG Diesel Propylene Tomorrow: Power generation (SOFC) Chemical intermediate Gasoline Key Messages Dramatic progress has been made in the first 10 years in understanding and advancing the DME business Proven manufacturing technologies Large, high value fuel markets Robust economics Coal and biomass gaining importance as primary fuel DME is fastest growing methanol derivative DME has become a COMMERCIAL REALITY DME is a commercial LPG blend stock in China Chinese companies rapidly gaining production, distribution and marketing experience The next few years is DME s moment of opportunity. IDA aims to help seize it 22

23 H/ORatio Thank you for your attention Please visit our website: By-products from the Reaction CH + H O CH OCH +... X Y 3 3 Water 2 SMR H/O Ratio (Y) 1 CO 2 CO 2 addition H O + CO 2 2 H 2 O ATR H + H O 2 2 POX/gasification Oxygen 0 0 Coal 2 Liquid Hydrocarbons H/C Ratio (X) 4 CH 4 23